ALIPHATICAND AROMATIC

HYDROCARBONS

Structure
1 5.1 1 n~rodilctioli
Ob-jectives
15.2 Reactivity of Aliphatic Hydrocarbons
15.3 Acidity of Alkynes.
15.4 Reactions of Ulisatilrated Hydrocarbons
Addition of Hydrogen Halides
Addition of Water '
Addition to Co~ljugatedDienes
Free Radical Addition Reactions
15.5 Aromatic Hydrocarbons
Structure of Benzene
Resollance and Aromaticity
Ozollolysis
tlydroxylation
15.6 Reactions of Aromatic Co~iipounds
Friedel-carftsAlkylation
1 5.7 Effect of Substitilents on Reactivity and Orientation
Effeet of Substituents on Reactivity
, Effect of Substituents on Orientation
15.8 Polyni~clearHydrocarbons
Naphthalene

-15.1 INTRODUCTION
In last two i~nitsyou have studied some important basic concepts of organic
chemistry. In this itnit we will discuss the clielnistry ofaliphatic and aromatic
liydrocarbons. The term hydrocarbon is used to designate organic co~npoundsof
carbon and hydrogen. The hydrocarbons provide tile basic skeleton for all organic
compoi~nds.First we will discirss the reactivity of aliphatic liydrocarbons and their
important reactions, then we will study tlie structure of benzene, aromaticity and
some reactiotis of benzene and polynuclear liydrocarbons.
Objectives
After studying tliis unit, you should be able to:
explain tlie reactivity of hydrocarbons
disci~sstlie meclianism of electropliilic addition reactions of alkenes and alkynes
explain the 1,2 and 1.4-addition of dienes,
explain the mechanism of free radical addition reactions,
explain the resonance et;ergy and aromaticity and
discilss tlie important reactions of aromatic compounds
Chemistry of Carbon 15.2 REACTIVITY OF ALIPHATIC HYDROCARBONS
Co~npounds
Alkanes are relatively unreactive to most of tlie common reagents. It is difficult to
define the terms "reactive" and "unreactive", since a compound may be reactive
under one set of conditions and unreactive under another. This reactivity or
unreactivity may be explained by considering the nature of C - 4 and C-H bonds
present i n their molecules. Since the electronegativities of carbon and hydrogen do
not differ appreciably. the bonded electrons in C-H are more or less equally
shared between them. Thus, C-H bonds encountered in alkanes are almost
nonpolar and the same is true for C - 4 bonds. Thus, polar and ionic reagents find
no sites to attack an alkane molecule. Alkanes undergo mainly substitution reactions,
which can be explained using free radical chain mechanism. These reactions take
place in the presence of uv light or at a high temperature or in the presence of
certain free radical initiators such as peroxides. In substitutio~ireactions, one or
more of the hydrogen atom(s) of alkanes are substituted by halogen or some other
groups.
Alkenes and alkynes are more reactive than alkanes. Most reactio~isof alkenes or
alkynes occur when the electron-deficient substance (an electrophile) attacks tlie n:
bond. By contrast, there little tendency for a double or a triple bond to react with
a electron rich substance i.e. nucleophile.
In addition reactions of an alkene, the n: bond is broken and its pair of electrons is
used in tlie formation of two new o bonds. The sp2 liydridised carbon atoms are
reliybridised to sp3 in the process. Compounds containing k bonds are usually of
higher energy than those having o bbnds. Co~isequently,an addition reaction is
~lsi~al
ly an exothermic process.

In the region of tlie double bond there is a cloud of n:-electrons above and below the
plane of tlie bonded atoms. The n: electrons are loosely held by the nuclei and are
thus easily available to electron seeking reagents. Such reagents are called
electrophilic reagents or electrophiles and the reactions are called electrophilic
addition reactions.
In general, alkynes undergo almost the same types of reations as alkenes. Electron
density around the carbon-carbon triple bond is higher than that of around carbon-
carbon double bond. So, we might expect alkynes to be more reactive towards
electrophilic reagents than alkenes, but tlie reverse is true, i.e., alkenes are more
rective than alkynes. You may be surprised at this trend. To understand the reason,
consider the nature of the carbon atoms of alkenes and alkynes. You may recall that
in alkenes carbon ato1n.s are sp2 hydridised arid in alkynes, they are sp hydridised.
Since an sp hybridised carbon is more electronegative than an sp2 liybridised carbon
atom, the n: electrons are more tightly held by the carbon nuclei i n the former case
and, hence, they are less easily available for combination with an electrophile. Thus,
electropliilic addition at the sp hybridised carbon atoms in an alkyne should be less
facile.
Another explanation !nay be attributed to the formation of highly strained unstable
cyclic alkenyl cation from an'alkyne as compared to strain-free alkyl cation formed
from an al kene.
 Aliphatic and Aromatic
Hydrocarbons

Both these factors may account for the diminished reactivity of alky~iestowards
electrophilic addition.'~eforestudying the electrophilic addition reactions of alkenes
and alkynes, let 11sstudy the acidity of alkynes.

15.3 ACIDITY OF ALKYNES

Accol-ding to Bronsted and Lowry, an acid is a species that donates H+. In fact, any
c o ~ i i p o u ~containing
~d a hydrogen atom can act as an acid under suitable conditions.
Acid strength can be rneasured by ~neasuringdissociation constants and expressing
'the results as pKa value. Strong acids have lower pK3 values than weak acids. -.
Hydrocarbons are usually not regarded as acids. Nevertheless, we can corlsider the
removal of a proton from a hydrocarbon by a very strong base.

In this equation, the hydrocarbon acts as a Bronsted acid and the conjugated base is
a carbon anion or carbanion.
Approximate acidities of different types of aliphatic hydrocarbons have been
~neasuredand their,pKa values are given in Table 15.1.

Table 15.1 : ~ciclities'ofsome hydrocarbons

Type Example

A I kane 49
CH, CH, +H'
-
Al kene 44 CH2=CH, & C H 2 = C ~ + H f

-
Al kyne 25 CH =CH CH=C+H+

FI-omthe data given in Table 15.1, we can see that there is a significant difference in
- the acidity of alkynes and other hydrocarbons. The order of acid strength of these
hydrocarbons is :
CH E CH > CH, = CH, > CH,CH,
Conversely, the decreasing order of basic strength of the conjugate anions resulting
from these hydrocarbons should be:

C H ~ C H ~ > =C? HH >~ C H &

alkarlide alkenitle dkyt~itle
anion anion anton

This decreasing order of acidities and basicities of hydrocarbons can be explained as

fol lows :
Carbon Conjugated bases of alkanes, alkenes and alkynes have an electron pair in sp3,sp2
and sp orbitals, respectively. As we proceed from the alkanide anion to alkynide
anion, the s character of the hybrid orbital increases and p character decreases. The
alkanide anioli (sp3 hybridised) has 25% s character and 7 5 % cliaracter;
~ alkenide
anioii (sp2 hybridised) has 33.3% s character and 6 6 . 6 % ~ character; and alkynide
anion (sp hybridised) has 50% s character and 5 0 % character.
~ You have already
studied in your earlier classes that electrons in s orbitals are closer to the nucleus
than those i n p orbitals. Since s cliaracter is maximum in alkynide anion and -
mininu~nin alkanide anion, the electron pair should be held most tightly in alkynide
anion and most loosely in alkanide anion. Alkenide anion lies in between. In other
words, tlie electron pair in alkynide anion should be least available for protonation.
As you know, the basic strength is more if the electron pair is easily available for
protonation. .
'Therefore, in the above series, alkynide anion is tlie weakest base and alkanide
anion is the strongest base. Conversely, alkyne is the strongest acid and alkane the
weakest acid.
l'liis can be explained in another way also. On the basis of the above discussion, we
can say that tlie sp hybridised carbon would attract the electrons pair constituting
the C-H bond of an alkyne more than the sp2and sp3hybridised carbons in alkene
and alkane; respectivelJ. This implies that C-H bond in an alkyne would be more
ionic and has a tendel,cy to donate a protqn (Hf). Hence, ethyne would be more
acidic as compared to etliene or ethane.

SAQ 1 1

Arrange the following bases in the increasing order of basic strength and give
reason

15.4 REACTIONS OF UNSATURATED HYDROCARBONS

As ~nelitionedearlier, alkanes are less reactive, therefore we will not discuss tlie
reactions of alkane. Here we will discuss only few important reactions of
unsaturated hydrocarbons and their mechanism.
15.4.l.Hydrogenationof unsaturated Hydrocarbons .

Hydrogenation of carbon-carbon multiple bonds can be carried out in the presence

metal catalysts such as platinum, palladium or nickel. The finally divided catalyst is
shaken as a suspension with a solution of the alkene i n an organic solvent in the
presence of hydrogen gas (heterogeneous hydrogenation).
 Hydrogen and the alke~iefirst become associated with the metal surface. Hydrogen Aliphatic and Aromatic
Hydrocarbons
is then transferred to the unsaturated carbons of the organic molecule. The two
liydroge~isare added on the same side (syn-addition) of tlie alkene.
So~iiecatalysts like tris (triphenyphosphine chlororliodium [RhCI(PPli,),], called
Wilkinson and Fisher were
Wilkinson catalyst, can be used for homogeneous hydrogenation. Wilkinson catalyst
given Nobel Prize in 1973 for
is niore selective and can be used to reduce less substituted double bonds in the
their work in transition metal
oresence of more substituted double bonds. chemistry.

1 Like alkenes, alkynes also undergo catalytic hydrogenation. Addition of hydrogens to

I an alkyne takes place in two steps. The first addition results in the formation of an
alkene; since an alkene call also undergo catalytic hydrogenation, the second
addition gives an alkane. By using a calculated amount of h y d r s n and a poisoned
catalyst, hydrogenation can be stopped at the alkelie stage. The catalytic poisons
I selectively block hydrogenation of alkenes.

. R \ C = C/ R
'
Polsoned catalyst
RCECR
Alhyne Pb-CI BaSOp
u-
' / H
1.2
t cis-A lkene

This is a stereoselective addition reaction giving predomina~itlycis alkenes. In the

absence of a poison, catalytic hydrogenation of an alkyne gives the alkane.

~ ~ ~ y NOI'OISOII
n e *lkalle
95% yield

Can we modify the reduction of alkyries so as to get only trans alkenes? The
answer is yes; we can get only trans products, but with a different reducing agent
and through a d ifferelit mechar1ism.
1 If we carry out the reduction of an alkyne with sodium metal or lithium metal in
liquid ammonia, trans alkene is almost the exclusive product. For example,
I 3-lieptyne is reduced to trans-3-heptene in this way:
j
I CH3CH2CH2 \
CH,CH,CH,C = CCH ,CH3 ' N" "'""' NH' f C = C/H
?-Heor\ lie 2 H,O U/ \c'u_I'u.

111the tirst step of this mechanism, the alkyne accepts one electron to give a radical
anion. The rhd ical anion is protonated by tlie am~ioniasolvent to ggive'an alke~iyl
radical; which gets further reduced by accepting another electron to give an alkenyl
anion. This species is again protonated to give the alkene.
Chemistry of Carbon
Compounds
RCECR
Na or LI
~ R C = C R -NH,
N H 3 t
I
~ ~ = &
Na or LI
,&=eR
Alkyne Radical Alkeynl
anlon Alkcnyl
radical anton .

Formation of the trans alkene is due to the rapid equilibration of the intermediate
alkenyl radical between the cis- and trans-forms. The equilibrium lies on the side
of the more stable trans species.

H\ c=i: --------1
7
R' R'
radical
cl~ tra11.cradical
(less stahle) (mow stahlc)

15.4.2 Reactions of Hydrogen Halides with Alkenes and Alkynes

Alkyl halide is formed when an alkene reacts with hydrogen halide. This reaction
is known as hydrohalogenation. The order of reactivity of HX towards alkene is :
HI > HBr > HCl > HF
In the case of an unsymmertrical alkene we get two different products. Actually
only one of the two products is formed in significant amount. For example, when
HBr adds to an unsymmetrical alkene like propene, in principle, two products could
be formed, i,e., 1-bromopropane and 2-bromopropane.

2-Bromopropane

CH,CH = CH2 + HBr

Pr opene

H
I -Brornopropane

However, only one product, 2-bromopropane is produced in significant amount.

One would like to know why only one product is formed. A Russian chemist
Vladimir Markownikoff studied this question in 1870 and made a generalisation
based empirically on his observation. According to the rule named after him as,
Markownikoffs rule, the addition of a hydrogen halide to an unsymmetrical alkene
-takes place in such a way that the positive part of the addendum goes to the carbon
atom that contains more number of hydrogen atoms.
However, when both carbon atoms forming the double bond have the same number
of hydrogen atoms in an unsymmetrical alkene, a mixture of products results. For
example, when 2-pentene reacts with hydrogen bromide, it gives a mixture of
2-bromopentane and 3-bromopentane.
 Aliphatic andAromatic
~r Br Hydrocarbons
I I
CH,CH,CH = CHCH, + HBr--+CH,CH,CH -CHCH, +CH,CH,CH- CHCH,
I

Markownikoffs rille call be explained on the basis of relative stabilities ofthe

carbocations. In the first step i.e., the additian of Hf to propene, tliere is a possibility
of the for~nationof eitlier primary or seco~idarycarbocation. Since the secondary
carbocation is Inore stable, it will be formed exclusively, resulting in the formation of
2-bromopropane.

+
CH3CH-CH2 Br- >CH3CH - CH2
I I I
H Br H
More stable 2-Rromopropane
I I+
CH, - CH = CH2 1-
>* I CH3yH -CH2
t
Br- + CH3CH-CH2
I I
H H Br
Less stable I -Rromopropane

Now consi'der another example, viz.,addition of HBr to propenenitrile.Addition of

HBr to propenenitrile gives I -brornopropanenitrile as the major product, which is
obtained from the primary carbocation.

H Br H
+
FNCCH-LH,
I
B;,NC&H-CH,
scc Cnrbocatlon

. H H Br
I f I I
NCCH - CH, '31
r N C C H - CH,

In the case of propenenitrile, because of the strong electron withdrawing effect of

the nitrile group, tile secondary carbocation is less stable than primary carbocation.
Furtlier the carbocation is separated from the CN group by two carbon atoms and
the destabilisation by the inductive effect is less.
Chemistry of Carbon Thus, the Markownikoffs rule can be modified to the following statkment -"In the
Co~npounds addition of hydrogen halide to alkenes, tlie more stable carbocation is formed which
then adds the negative ion to form the product." This rule is adequate to predict the
orientation pattern of addition of u~lsymmetricalreagents to unsymmetrical alkenes.
However, it may be eniphasised that this rule is applicable only to tlie addition of
electrophilic reagents.
The products formed from the addition of HBr to some substituted alkene are given
in Table 15.2.
Table 15.2 :Orientation pattern for addition HBr to substituted ethenes

Alkene Maior Product

C,H, CH- CH,

1
Br

CICH-CH,
I
Br

Entry 4 of Table 15.2 is of special interest and illustrates certain general features.
I n cliloroetliene (and other Iialoetlienes), the primary carbocation should be more
stable due to iiiductive effect (similar to the addition of HBr to propenellitrile given
earlier) but tlie reverse is true. Because inductive effect is not the only effect in
operat ion.
Br

r
I
CI ;H - CH, "- t CI CH - CH,
ser. I-Bro~no-I-cl~lom-etl111e
CAIbocatio~i

ClCH = CH, + H B r

i
A
pri. Carbocation .
Br
1 -Bromo-2-chloro-ethane
There is, however, another effect arising from detocalisation of the lone pair on the Aliphatic and Aromatic
Hydrocarbons

-
chlorine atom with the vacant p-orbital of carbo~itionat C-2 (resonance effect)
which stabil ises the secondary carbocation.

-4
* +
CI - CH,- - CH,
+
CI = CH, - CH3
+
C'1 - CH, - CH, .%, - No resonance structure
I -

The question is, which of these effeets predominates? Forination of l-bromo-l-

cliloroethane implies that the lone pair effect apparently prevails over the inductive
effect rendering secondary carbocation more stable than the primary carbocation.
Rearrangement : Rearrangement is one of the characteristics of a carbocation. A
carbocation formed, in an addition reaction of a hydrogen halide to an unsymmetrical
alkene, often undergoes rearrangement (alkyl or liydride shift) to give a more stable
carbocation. For example, addition of HCI to 3,3-dimethyl-I -butene gives two
products, 2-cliloro-3,3-di~netliylbutane
(normal product) and 2-chloro,
2,3-dimethylbutane (rearranged product) as shown in following scheme:

S1.c Carbocation
(less stable)

CK;-
k11.Carbocatio~i 2-Chloro-2-
(~iiorestable) 3-d~methylbutane

Alkynes also undergo liydrohalogenation. Like alkenes, the addition is in accordance

with Markownikoffs rule. For example, ethyne reacts with hydrogen bromide to
form first I -bromoethene and then I, 1 -dibromoethane.

HBr I
CH CH -----+CH= CH HBr %CH,-CH
I I I I
H Br H Br
P
The mechanism of the reaction is same as in the hydrohalogenation of alkenes.
Additio~bofone ~noleculeof HBr gives bromoethene.
Cl~emistryof Carbon
Compounds

Addition of another molecule of hydrogen bromide could give either secondary

carbocation or primary carbocation. Since the secondary is more stable than the
primary, the reaction proceeds via the former to form 1, 1 -di bromoethane, i.e.

c* I H2 - CHBr a C H I - CHBr
pri. Carbocation

Because of the electron withdrawing nature of bromine atom, the availability of n

electrolls in I -brornoethene is less than that in ethyne. Hence addition of HBr to
I -bromoethene is much slower than to ethyne.
SAQ 2
Predict the relative rates of the following alkenes towards HBr and give reason.
a) CH,CH,CH=CH, b) CH, = CH, c) CH3CH2CH=C(CH3)2

--------------------------------------------------------------------------------------------------
15.4.3. Reactions of water with alkenes and alkynes
I n the presence of a mineral acid, water adds to the alkene to gives an alcohol. This . I
reaction is called hydration of an alkene.
I

I
This reaction also follows Markownikoffs rule, a pattern with which we are now
familiar. As expected, the reaction occurs in two steps. The alkene is first
protonated to give a carbocation. Attack of the nucleophile (H,O) on the
carbocation, in the second step, and loss of a proton from the resulting adduct
completes the reaction.
 Aliphatic and Aromatic
Hydrocarbons

?+
H-OH

I
..
Protonated
H alcohol

Since a carbocation is involved, rearrangement is possible. Carbocation can undergo

a 1.2-shift of CH3 group to yield the more stable tertary carbocation, i.e.

+
-.I -3

,CH3- C- CH-
6~~
Another metl~odused to accomplish Markownikoffs hydration of an alkene is ,
oxymercuration-demercuration. Alkene reacts with mercuric acetate in the
presence of water to give hydroxy-mercurial compounds which on reduction
accomplishes de~nerci~ratio~l and produces an alcohol. The product of
oxymercuratiori is ~ ~ s ~ ~reduced
a l l y with sodium borohydride (NaBH,).
Oxyniercuration-demercuration reaction usually gives a better yield of alcohols than
acid catalysed hydration.

Ii
CH,CH,CH = CH, + H,O -t- Hg(0 C CH;),
I-Uulelie Mercuric acetate

+
Mechanism: First mercuric acetate dissociate into H gO,CCH, and 02 CCH3 e.g.,

+
In the first step electrophile (H g02CCH3) attacks,the carbon-carbon double bond
and forms a cyclic intermediate called acetoxymercurinium ion.

I I + 16+ 1
- C =C- + Hg02CCH3---+ -C - C
..... 1
-

+
; HgO,CCH,
Acetoxy~nercuriniumion

In the next step nucleophile (H,O) attacks on the partially positively charged carbon
atom from the side opposite tomercury, to give the stable organomer~ur~
compound. The organolnercury compound on reduction with NaBH, gives alcohol.
Cllemistry of Carbon Oxymercuration is regiospecific and stereospecific (antiaddition) rea :tion. The
Compol~~lds stereospecificity is attributed to formation of a cyclic intermediate.
Like alkenes addition of water to alkyne should give alcohol, e.g.,
Regiospecific: only one of
the two direction of addition
is observed.
The alcohol produced by hydration of an alkyne, however, is of a special kind known
Streospecific: A reaction in as enol. As the name (en-01) indicates it has OH group attached to a carbon atom
which stereo isomeric for~ninga double bond. Infact enols arevery unstable and generally undergo
starting ~naterialgives isomerisation (tautomerism) to give either an aldehyde or a ketone.
stereoisomericallydifferent
products.

.
Enols are converted to aldehydes or ketones by prototropic shift, i.e., shift of a
proton from'oxygen to carbon atom. This phenomenon is known as keto-enol
tautomerism, and the individual co~npoundsare known as tautomer. For
example, when ethyne reacts with water, it gives ethanal, an aldehyde, wl-tile
I -propyne gives propanone, a ketone, i.e.,

I
OH 0
ell01 Etlianal
(Aldehyde)

I i
I'r opyne
OH 0
enol Pr opanone d
(ketone)

The en01 is converted into aldehyde or ketone by a lnechanis~nthat is similar to

hydration of a double bond. The en01 double bond is protonated to give a
carbocation. The carbocatio~lin this example, as its resonance structures show, is a
prototlated ketone. Instead of adding water, this ion loses a proton to give ketone. I
RC -CH2----, uRC-CH,
I Protonated
Ketone

L +
H-OH,

RC- CH, +H,Of

0

You mav now ask why the carbocation is not attacked by a water molecule to give I

I
L
H,O
.. 'OH 2
 The answer is that this reaction is reversibl~and the:equilibrium between the ketone ~ l i ~ h a tand
i c Aromatic
i
I
and the corresponding diol in most cases favours ketone. Hydrocarbons
I

;Alkynes cannot be hydrated as easily as simple alkenes, because of their lower

reactivity towards electrophilic reagents. However, in the presence of mercuric
sulphate, a catalyst, hydration occurs readily. A possible explanation of the function
of the catalyst is that Hg++ion being of a large size, readily forms a bridged ion, a n
complex, which then reacts as shown below: , - --
a

15.4.4. Addition Reactions of Conjugated Dienes

Before studying the reaction of conjugated dienes we must recall the structure of
I
I the diene.
Let us consider 1,3-butadiene as an example of a conjugated diene,

Each of the four carbon atoms of butadiene contains an unhybridisedp-orbital. The

sdieways overlap of unhybridisedp-orbitals gives rise to two localised n bonds, i.e.,
the bonds between C, and C, and C, and C, (Fig. 15.1). The four carbon atoms and
the six hydrogen atoms of butadiene lie in the same plane so that there is a certain
amount of overlapping between the electron clouds of the p-orbitals of C, and C,.
This give rise to completely delocalised n-orbitals spread over all the four carbon
atoms. It is this delocalisation of n electrons which imparts stability to 1,3-
butadiene.

Fig. 15.1 : Orbital structure of 1,3-butadiene

In isolated diene both the double bonds react independently, as though they are in
different molecules. Reaction of an isolated diene say 1,4-pentadiene with bromine
gives 4,5-dibromo-1-pentene. i.e.
 Chemistry ofcarbon
/Compounds

Conjugated dieries behave differently from isolated dienes. Conjugated dienes

undergo normal ah.well as unexpected addition reactions. When a conjugated diene,
say 1,3-butadiene is treated with bromine, two dibro~noderivatives are obtained.
One of these is the expected 3,4-dibromo-1-butene due to 1,2-addition and the other
is the unexpected 1,4-dibromo-2-butene due to 1,4-addition (major product).

Similarly reactions of HCl and H, with conjugated diene provide not only 1,2-
addition product but also 1 +I-addition product, e.g.

Addition at 1,2-position is understandable but how can we account for the products
that are obtained due to 1,4-addition? To understand this, let us examine the
~necl~a~iism of the addition of hydrogen bromide to 1,3-butadiene. The first step
involves the formation of carbocation. Hydrogen may attach itself to either C, or Ci.
Tlie addition ofthe hydrogen at C, would give rise to an unstable primary localised
carbocation. But the addition at C, results in the formation of resonance stabilised
allyliccation. This also explains the enhanced reactivity ofdienes over isolated
double bonds.

r
I +
CH,= CH- CH - C H 2
Icss stable

Allylic carbocation
(plore stable)

In the second step B? can attack at either C, or C, since both share the positive
charge. Thus a mixture of 1,2- and 14-addition products is obtained.
 H Br H Br H Aliphatic and Aromatic
I
Rr I I I I Hydrocarbons
CH-CH 2 ,CH2 = C H - C H - C H 2 + CH, - C H = C H - C H ,

Now one can ask whether these two products are formed in equal amounts or in
different ratio. It is interesting to note that the product composition in these
reactions varies at different temperature. To understand this take the example of
addition of HBr to 1,3-butadiene. HBr when added to 1,3-butadiene at low
temperature (I95 K), the 1,2-product (80%) predominates over 1,4-product (20%).
While at higher temperature (3 15 K) the 1,4-product (80%) predominates over 1,2-
product (20%). At intermediate temperature, mixtures of intermediate cofnposition
are obtained.

I
CH, - Cfl -CH = CH,
k 1
Rr

CII, - CII =CII - CII,

B $r

It has also been observed that the 1,2-product on warming to 3 15 K with a trace of
acid results in an equilibrium mixture in which 1,4-product predominates.
How can we explain these observations? Let us examine the reaction by drawing a
potential energy diagram (Fig. 15.2). At low temperature, the addition of HBr to 1,3-
butadiene gives 80% 1,2-product. This.shows that 1,2-addition has the low energy
of activation (EaJ and thus, the 1,2-product is formed faster than the 1,4-product.
The relative rates of the reaction control the product ratio at a low temparature.

1:2-Addition 1,J-Atld~rton
product product

1
- Progrcss ol' 1,2-addition -
Progrcss of I,4-addi~ion

Fig. 15.2 Potential energy diagram.

At higher temperature, a greater percentage of molecules can reach the higher-
energy state, and the more stable, 1,4-product predominates. At higher temperature,
<'hk::nistry of Carbon the relative stabilities of the products control the product ratio. Thus, we can say
:,'cia~poands 1,2-product is kinetiially controlled while the 1,4-product is thermodynamically
controlled.
Formation of 14-product c?n also be explained on the basis of electrometic effect.
Rutadiene can undergo the electromieric effect in two stages.

Second ionic species is more stable as the charges are further apart in this as
compared with the first. In an ionising solvent, the addition of Br, takes place in the
second species to give 1,4-addition product.

SAQ 3
Fill in the blanks :
a) When a conjugated diene is treated with halogen it gives normal ............
product and unexpected ............product.
b) Addition of H+ to 1,3-butadiene gives ............ carbocation and ............
carbocation.
c) When HBr is added to 1,3-butadiene at low temperature ............predominate
and at high temperature ............ predominates.
d) In the addition of HBr to conjugated diene the ............is kinetically controlled
and the ............is thermodynamically controlled.

15.4.5Free Radical Addition Reactions

The above discussion may give you the impression that addition of hydrogen
halides to unsaturated hydrocarbons always gives Markownikoffs product. But it is
not so. After extensive study of the mechanism of addition of HBr to different
alkenes, it was found by Kharasch and Mayo that in the presence of a peroxid; the
product obtained was contrary to Markownikoffs rule. Such additions are
sometimes referred to as anti-Markownikoff additions. Since the orientation is
reversed in the presence of a peroxide, tkis is also known as the peroxide effect.
For example, the addition of hydrogen bromide to propene - - in the presence of
pero~idesgives
1-bromopropanerather than 2-brmopropane. However, this effect is not observed
with HCI or HI.
 Aliphatic and Ai-ornxtic
Br Hydrmrh?ns
No Peroxide I
9 CH3 CHCH,
2-Bromoprope

HBr

. Br
I
L CH,CH2C H2
I-Bromopopane

The intermediatein the peroxide catalysed reaction is a free radical and not a
carbocation, The function of peroxide is to generate the free radical
a
(RC02)2--+2RC02 4 2 R+ 2C02

R+HB~-RH+B~
Bromine radical can add to either of the two carbon atoms producing either a
primary or a secondary radical.
The bromine radical prefers to react at the terminal carbon to give a secondary
radical because, the secondary radical is more stable than a primary radical. The
orientation ofaddition ofthe free radical is controlled on the principle that it takes
place in a manner such that the more stable radical, of the possible alternatives, is
generated. Consequently, the final product of reaction of HBr is (in presence of
peroxide) generally the one with bromine attached to the less substituted carbon -

Now let us take the example of propenenitrile. How would propenenitrile react with
HBr in the presence of peroxides? Reaction of propenenitrile with HBr both in the
presence as well as and in the absence of peroxide yields I -bromopropanenitrile

H Br H
No Peroxide + I I I
-
2 CH2CH-CN Br- ,CHI-CH-CN
I -Bromopropanenitr

. HBr
CH,=CH-CN I

Peroxide
5 CH$H-CN
I
Br
- H-Br
CH2 - CH -CN
I
Br
I
H
I -8romopropanen

we see t"at the same product formed by an entirely different mechanisms, On*he
basis Of the principleJdiscussedabove, it is possible to PrsdjEtfie
in either case. of
Chemistry of Carbon 15.4.6. Hydroboration
Compot~nds
In hydroboration diborane, (BHJ2 adds to a carbon-carbon multiple bonds to yield
an organoborane.Addition of borane to alkenes gives alkyl boranes while addition of
borane to an alkyne gives alkenyl borane.

\ / I I
C = C + B H 3 -H-C-C-BH,
/ \ I I
Alkyl borane

I I
-CsC-+BH3 j H-C=C-BH2
Alkenyl borane

This reaction is very facile and requires only a few seconds for completion at 275 K
and gives organoboranes in quantitative yield in ether solvents. The addition takes
place in a stepwise fashion via successive addition of each boron hydrogen bond to
the al kene. The sequence of reaction is called hydroboration.

H H
I 1
step 1 CH2 =CH2 + B- H ----+ H - B- CH2CH3
I
H

I
Step2 CH2 =CH2 +H-B-CH2CH3 ---+ H - B -CH2 -CH,

H CH~CHB
I I
Step 3 CH2 = CH2 + B - CH2CH3 + B - CH2CH3
I I
CH2CH3 CH2CH3
Triethyl borane

Sometimes the hydroboration reaction is described an anti-Markownikoff s addition.

This is true only in a literal sense, because in this reaction hydrogen is the
electronegative portion ofthe molecule instead of being the electropositive portion
as in other cases. The result appears to be anti-Markownikoffs addition, for
example

CH3CH =CH2 --+CH3CH- CH2

k L
H-BH2
b S
H
1
AH^
The organoboranes are versatile compounds capable of undergoing a variety of
chemical transformations. Some important reactions of organoboranes are given
below :
i) Oxidation of an organoborane by alkaline H202gives the corresponding alcohol.

3CH,CH2CH = CH, BH3 , ( C H ~ C H ~ C H ~ C H ~H202"H

)~B- *
3CH3CH2CH2CH20H
1 - Bu tan ol
 Aliphatic and Aromatic
Hydrocarbons

i i ) Oxidation of organoboranes with chromic acid yields carbonyl compounds.

0
It
CH;CH = CHCH, +CH,CHCCH,
iii)l'he acid-hydrolysis of organoboranes provides a useful method for carrying
'%
out liydrogenatio~iof alkenes and alkynes.

,CH,COOH
3CH,CH=CH, (BH')2 b (CH,CH~CH~),
B > 3CH,CH2CH,
Propane

-C.C- 2
2.
I .( B H ~
-CH=CH-
al
CH3COOH cis kene

iv) Reaction of trialkyl boranes with alkaline silver nitrate solution induces a
coupling I

reaction and hence provides a method for the synthesis of higher alkanes.
CH
1 3
AgNO ,I NeOH
3 ), CHCH 2 1, B
~[(cH 275 K 3 CH3CHCH2CH2CHCH,
2.5-Di1nethyll1e xaue

15.5 AROMATIC HYDROCARBON - -

I n addition to the aliplialic compounds there were large number of another type of
'.compounds. which were arbitra;ily classified as aromatic compounds. Benzene, the
siniplest of the aromatic cdmpounds, was isolaled by Michael Faraday in 1825 from
the &s obtained by pyrolysis of whale oil. Later in 1845, Holman discovered benzene
in coal tar, wliicli co~itainsbenzene and many of its derivatives.

Many compounds isolated from natural sources,andmany synthetic drugs are aromatic
in nature. The local anaesthetic procaine and the tranquiliser diazepam (valium) are a
few examples. Benzene is carcinogenic and injurious to health. Prolonged exposure
leads to bone-marrow depression. Benzene as a solvent should, therefore, be used
carefi~lly,avbidi~igeviporation in the oljen or inhaling its vapour. .
Keeping in view the i~nportanceof aromatic compounds, we shall study the chemistry
, of benzene and its derivatives in this unit. Let us first discuss the structure of benzene.

15.5.1 Structure of Benzene

Accordi~igto niolecular orbital theory, benzene is a planar flat symmetrical
i ~ l e thc shape of a regular hexagon. The C-C-C bond angle has a value
~ ~ ~ o l e chaving
of 120". Each carbon atom in the ~noleculeis sp2hybridised. ~woorbitalsof the sp2
liybridised carbon atom overlap witli the other two orbitals of the adjacent carbon
atoms resulting in the formation of two o bonds. The third orbital of each carbon
atom overlaps witli 1 s orbital of hydrogen atom to forms a o bond.Each carbon '

atom still has a p orbital perpendicular to the plane of the ring. Thep orbital has two
lobes one above and the other below the plane ofthe ring and because all p orbitals
are equivalent, they overlap equally well with both the neighbouringp orbitals
resulting in a delocalised dough~utshaped 7c orbital cloud above and below the ring.
Chemistry of Carbon The picture that emerges out of this discussion is given below in Fig. 15.3.
Compounds

o-skeleton rr-skeleton

Fig. 15.3 :a and rc skeleton of benzene .

The benzene ring is a cyclic conjugated system and is usually represented as a
regular hexagon with a circle inside the ring. This gives an idea of delocalisation of
.n-electrons.

15.5.2Resonance Energy
You have already studied the basic concept of resonance in Unit 13. Here we will
discuss the resonance energy in aromatic compounds and aromaticity.
The structure of benzene gives the impression that it is a cyclic compound of six
carbon atoms containing three single and three double bonds. If this were so, you
would expect two values of carbon-carbon bond lengths, viz., one for single bonds
(nearly 154 pm as in efhane) and the other for double bonds (nearly 133 pm as in
ethene). Experimental evidence through X-ray diffraction studies shows that all the
six carbon-carbon bonds in benzene are equal and have a length of 139 pm, which
is in between 133 and 154 pm. The explanation of this is as follows :
The heats of hydrogenation of cyclohexene and benzene determined experimentally
are given below :

cyclohexene -cyclohexane

cy clohexatriene cy clohexane
(benzene)

The heat evolved when hydrogen is added to cyclohexene (hiving one C = C bond)
is 121 kT mol-'. The expected value of the heat evolved when hydrogen is added to
benzene (having three C=C bonds) should be 3 x 121 M mol-I = 363 M mol-I, but
the experimental value is 209 W mol-'. We can infer that benzene is more stable
(having lower energy content) than the hypothetical molecule containing three
isolated C=C bonds by 363 - 209 = 154 M mol-'1. This energy difference is called
the resonance energy and is responsible for the stability of benzene compared to
other unsati~ratedcompounds which lack resonance stabilisation (Fig. 15.4) Aliphatic and Aromatic
Hydrocarbons

l lypothetical

I/?
I
-I'rogress of waction--+ -Progress of reaction*

Fig. 15.4 : Energy diagrams for the hydrogenation of cyclohexatriene (hypothetical) and benzene

15.5.3 Aromatici ty
Your student may ask you whether other cyclic compounds with x electrons might
also be considered aromatic. The answer is no. Not all the cyclic compounds with x
electrons are aromatic but some of these systems are indeed aromatic. What
structural features are necessary for a molecule to be aromatic?
A German Physicist, Erich Huckel in 193I, proposed a rule called the Huckel's rule.
According to this rule, an aromatic molecule must be a cyclic conjugated species
having (4n+2) x-electrons where n is an integer (n = 0,1,2,3......). This means that
only tlie ring with 2,6,10,14,...... x electrons may be aromatic but a ring with 4,8 or
12 x electrons can not be aromatic, Huckel's rule is also applicable to ionic species.
Let us look at some of the evindences supporting the Huckel's rule.
1) Cyclobutadience

no. of x-electrons=4
4n+2x-electrons are required for aromaticity.Cyclobutadiene has 4 x-electrons, hence
cyclobutadiene is not aromatic as it has 4 x-electrons and is highly unstable.
2) Benzene

Here tlie 4n+2x rule can be applied as it has 6n-electrons which are required for a
single ring system. It is an excellent example of an aromatic system.
3) Cyclooctatetraene

no. of x-electrons=8
It does not liave 4n+2x electrons and thus is not aromatic.
;-
Chemistry of Carbon Another reason why cyclooctatetraene is not aromatic is that it is not even fully
Colnpounds conjugated, It is a tub shaped molecule in which there is no cyclic conjugation and the
neighbouring orbitals containing the R-electron do not have the necessary geometry
for proper overlap.

cyclooctatetra~lce
From the above example, it is clear that a flat planar geometry is required for proper
overleap resulting indelocalisation of R-electrons which is a necessary condition for
aromaticity.

15.6 REACTIONS OF AROMATIC COMPOUNDS

Characteristic reactions of benzene involve substitution, in which the resonance-
stabilised ring system is preserved. Electronphilic substitution includes a wide variety
of reactions, such as nitration, halogenation, sulphonation and the Friedel-Crafts reactions
undergolle by nearly all aromatic rings. Some important reactions are summarised in
Table 15.3. Here we will discuss only few of them.
Table 15.3 :Electrophilic aromatic substitution reactions

Reactions Remarks
1) Nitration Formation of NO; :
Speciesyroducinp NO: are
+
+ + + ArH + HNO, H2S04 ) ArN02 + H 2 0 H,SO, + HONO, H20NOZ+ HSO;
NO2 BF4 .N 0 2 NO;.N02 C104
2) Halogenation H,~NO, + H,O+N&

A~H+X,&A~X+HX Reactivity :
3) Suphonation 1, < Br, < CI,
ArH + SO, + ArS0,H + H 2 0 Formation of SO, :
+
4) Friedel-crafts alkylation 2H2S0, -SO, + HSO; + H, 0

5) f friedel-Crafts acylation
+ HCI
+ RCOCIA~C"A~COR
A~H
Note : Ar = C,H;

15.6.1 Friedel-Crafts Alkylation

Alkylation of benzene is the substitution of hydrogen by an alky group in the ring.
Reaction ofthe aromatic compounds with alkyl halides in the pressence of anhydrous
AICI, as the catalyst gives alkylated products. This reaction is known as Friedel-
Crafts alkylation. The reaction of 2-chloropropane with benzene in the presence of
AICI, to yield (I-methylethyl) benzene is a typical Friedel-Crafts alkylation reaction.

0 + (CH3hCHCI
2-chloropropane
h 0 CH(CH,),
+ HCI

( I -methylethyl) benzene
The electrophile in the Friedel-Crafts reaction is R+.Thision is formed when an alkyl Aliphatic and Aromatic
halide reacts with a Lewis acid. Lewis acids such as AIC13,FeC13,ZnCl,, AIBr,, BF, Hydrocarbolls
etc. are used in Friedel-Crafts alkylation. In case of alkylation with tertiary alkyl halide
the electrophilic species is a 'free carbocation. However, in primary and secondary
alkyl halides, it appears that instead of free carboncations, the electr?philic species is
an alkyl hadide-Lewis acid complex with positively polarised carbon.

CH~
terf alkyl
halide

6' 6-
CH3CH2CI + AICl, ---+ CH, CH2C1.. . . . . AICl,
pri, alkyl halide alkyl halide Lewis acid complex

Though the Friedel-Crafts reaction is widely applicable in organic synthesis, it has

some limitations as given below :
(i) The main difficulty with the Fridel-Crafts alkylation is that the substitution of
the first alkyl group activates the ring towards further substitulion. ,We will
discuss activation and deactivation in latter in this unit.

The best way of avoiding this second reaction is to use an excess of aromatic compund.
(ii) Friedel-Crafts alkylations are limited to alkyl halides only; aryl halides and
alkenyl halides do not react. Aryl and alkenyl carbocations are too unstable to
form under Friedel-Crafts reaction conditions.

- No reaction

aryl halide

+ CH, = C H C I No~ reaction

alkeny l halide
Cl~emistryof Carbon (iii) If tlie aromatic compound has an electron withdrawing substituent, it does not
Compounds undergo Friedel-Crafts alkylation. It is because tlie deactivated ring is not reactive
to attack carbocations.

0 + RX AICI; , NO reaction

-
(iv) Aromatic a~ninesfail to undergo al kylation, probably because amino group forms
a complex with Lewis acid. Since this complex has a positive charge on nitrogen,
it deactivates the aromatic ring for electrophilic substitution.

0 0 RX
A,.,,
,No reaction.

(v) Sometimes during the alkylation, the attacking electrophile undergoes

rearrangement by 1,2 shift of H or R. For 'example, tlie alkylation of benzene
with chloropropa~ieleads to a mixture of propylberizene and (I-mcthylethyl)
benzene.
No rearrangemnt

06h[pl ---------- AICI, a 0 CH,CH,CH,

I (minor)

Rearrangement

+
-A'C14 5CH3C HCH, + AICI;

(major)

SAQ - 4

Wliat are the li~nitationsof Friedelkraft alkylation? Discuss them briefly with suitable
examples.
 15.6.2 ~ e n e i a Mechanism
l of E l e c t r o p h ~Substitution
~~' Aliphatic and Aromatic
Hydrocarbons
All the electrophilic substitutioh reactions take place by similar meachanism. It is
necessary to understand the principles of this mechanism. Thus, we will discuss the
general electrophilic substitution mechanism by using Efforelectrophiles.
Before studying detailed mechanism, let us briefly recall what we have learnt about
electrophilic addition to alkenes. Electrophilic attack on C=C gives carbocation
intermediate which is then attacked by ~~ucleophile
to yield addition product.

, - CI - CI-
- -
I I I I Nu-
-C=C- + E' 4-C-C-
.v I + I I
Nu

, An efectrophilic aromatic aubstitution reaction begins in a similar way. The n electrons

/ ofthe ring attack on electrophile E', forming o bond with electrophile.In this process,
the positive charge of the electrophile is to be transferred to the adjacent ring carbon
atom which b called carbocation. This is slow step and is, therfore, the rate determining
step.,

This carbocation is stabilised by reasonance as shown below :

These three resonance structures of the intermediate are often combined and
represented as follows :

In the case of alkenes, you have seen that nucleophile attacks the carbocation to yield
the addition product, Since, in the aromatic system, the addition of the nucleophile
would destroy the aromatic stabilisation ofthe benzene ring, this type of addition does
not take place in aromatic carbocation. Instead, nucleophile acts as base and abstracts
a ring proton yielding substituted aromatic product.
Chemistry of Carbon 15.7 EFFECT OF SUBSTITUENTS ON RJZACTIVITY AND
compounds
ORIENTATION
We have just seen that benzene undergoes electrophilic substitution reaction. Benzene
forms only one monosubstituted product by the electrophilic substitution. Let us see
what happen when we carry out an electrophilic substitution on substituted benzene.
Studies have shown that the substituents affect the reactivity and the orientation in
the benzene ring.Three possible disubstituted products, viz, ortho,para and meta can
result. These three products are not formed at random; rather, a given substituent
already attached to the benzene ring, usually directs the position of the second
substituent.
There are two types of substituents, one is electron donating groups, such as
- N q , -OH, -OR, -NHCOR, and alkyl and other is electron-withdrawing groups

which include halogens , - CHO, - COR, - cOOR, - CN, - N+ Oz , and - N+ R3

Now we will study the effect of substituents on reactivity and orientation.
15.7.1Effect of Substituents on Reactivity
To compare the rates of electrophilic substitution in benzene, methyl substituted
benzene (eleqtron donating group) and nitro substituted benzene (electron withdrawing ,
group) are compared in a reaction, say nitration. It is-found that nitration of methyl
benzene is more facile than benzene whereas nitration of nitrobenzene is more difficult.
In other words, benzene ring seem to be activated in methylbenzene and deactivated
in nitrobenzene. Let us see if we can explain this on the basis of intermiedate
carbocation formed.

In the case of methylbenzene (II), the methyl group, which is an electron-donating

group, tends to neutralise the charge on the carbocation. This dispersal of the charge I
stabilises the carbocation thus leading to faster reaction than benzene. 1
In case of nitrobenzene 0, the nitro group whichis an electron-withdrawing group
tends to intensify the positive charge and destabilise the carbocation. Due to this
effect, the rate of the reaction is lower than in benzene. Reactivity in electrophilii:
aromatic substitution depends upon the tendency of a substituent group to release or
withdraw electrons. A group that releases electrons activates the ring; a group that
withdraws electrons deactivates the ring. Hence, the order of reactivity of the above
-
compound towards electrophilic substitution reaction is:

15.7.2Effect of Substituents on Orientation .

, The second effect of a substituent is to direct the position of the incoming substituent.
Thus, for instance, nitration of phenol gives ortho and para nitrophenol as major
-A- products.
 6 6
6 6'0' N0,/HaSO, , +

-\ NO,
+

\
Aliphatic and Aromatic
. t
Hydrocarbons ~

o-nitrophenol m-nitrophenol p-nitrophenol

(45-50%) (Trace) (45-50%)

On the other hand, nitration of nitrobenzene yields meta dinitrobenzene as a major

product, i:e.

1
0
\
NO2

mg-so, , ON',+
\
6 NO* NO2

NO,
+ 0\
NO,

o-dinitrobenzene m-dinitrobenzene pdinitrobenzene

(7%) (9 1%) (2%)

This shows that different substituents have different effect on substitution reaction.
Thus substituents can be classified into three groups i.e.,
ortho and para-directing activator
meta-directing deactivator
ortho and para-directing deactivator
Table 15.4 lists some of the groups in each catergory,
Table 15.4 :Classification of directing effects for some common substituents
ortho- and para- ortho- and para- meta-directing
directing activators directing deactivators deactivators
!
-N H, -1 ' -N+(CH3)3
-OH 43r -NO,
1 -OCH, <I -CN
1 0
-N HCOCH3 -F II
-CCH3
1

Before we try to account for the orientation in electrophilic substitution, we should

clearify our definitions.ofactivingand deactivatinggroup.Activatinggroups activate all
the position of the ring. They Ire ortho and para directors because they activate
ortho and para position much more than they do the meta position. Similarly, deactivating
groups deactivates all position in the ring. They are meta directors because they
deactivate the ortho and para position more than they deactivate the meta position.
Chemistry of Carbon Thus, the effect of any group, whether activating or deactivating, is strongest at the
Compounds orthd and para positions.
Orfho- and para- directing activator :To undeFstand the orientation effect of the
substituents,we have to first write all the possible resonance forms ofthe cqrbocation
for each of the three possible reaction courses.
R e a c b m of NO,' at the para, meta and ortho positions of phenol give the
intermediates with the follwing resonance structures.

b) mefa- Attack

cj para- Attack r
 ,-
In case of orrho and para attacks, structures IV and X respectively show that the Aiiphatic arrd Aromatic
unshared electron pair of oxygen delocalises the positive charge on the carbocatior! Hydrwarbns
and hence, four resonance structures are possible, In the case of meta attack, since
the charge cannot be delocalised into the -OH group, the carbocation thus formud has
only thl-eeresonance structures, Hence, carbocation fromed by ortho andpara attacks
are more stable and, thxfore, ortho andpara nitrophenols are the major products.
Now take the example of electrophilicaromatic substitution on alkyl substituted benzene
ring. Let us inspect the possible resonance strutures of carbocation formed by the
attack of the electrophile NO,+, on toluene.
a) orilso-Attack

(b) metn-Attack

(c) pnro-Attack

I
I
CH,
I

Q+No;-Q

H NO,
-9-Q H No2 H NO,
+

1 As indicated above, in structures 111 and VIII, resulting from ortho and para attack
respectively, the positive charge is located on the carbon atom to which the methyl
group is attached. Since that is tertiary carbocation it is more stable than the others, i1-i'
which the positive charge at a secondary carbon. On the other hand, meta attack
produces an intermediate in which none of the resonance structure benefits from such
tertiary carbocation stabilisation. Thus, electrophilic attack on a carbon located at ortho
orpara to methyl group leads to cationic intermediate that is more stable than the one
derived by atttack at the meta carbon. Substitution at ortho andpara-position is, therfore,
preferred to meta substitution.
,
This can also be explained on the basirof inductive effect. The carbocations I11 and
VIII formed by the ortho and para attack respectively, are stabilised by inductive
effect of methyl group and, therefore, formed in major amount.
metn directing deactivators : We can apply similar arguments.to meta-directing

' ~[QUPS. These POUPS electrotring.

gative p o u p ~withait an UnShared pa;r
+
adj"d '0 the benzene
In a\\ hte. cases, the benzene ring would be
onbaEliyi
an Letus tke theDamp\t of &ation of nitrobenzene *he
,
b cahocation formed axe: I

,,,to9 0f the
Chemistry of Carbon a) ortho-Attack
Compounds
- - - -
t
0

6
\vO
+ No; H .

c) prrra Attack

-0
d+No;7Q-*Q H NO, H NO, H
+

NO,

In all tlie three cases, carbocations formed have three resonance structures, But the
structure I11 and VIIT resulting from ortho and para attack respectively, are very.
unfavourable because the positive charge is placed directly on the carbon carrying the
electron withdrawing group. A severe electrostatic repulsive interaction between the
. carbocation and tlie positive end ofthe nitro group strongly disfavours this carbocation.
The carbocations formed by meta attack, have no such form with similar charges on
adjacent atoms. Therefore, its transition state is the most stable, and attack at me&-
position is preferred.
ortlro and para directing deactivator : Halogens are unusual in their effect on
electrophilic aromatic substitution.They are deactivating yet ortho andpara directing.
For understanding the orientation, consider the attack of electrophile at ortho, meta
and para positions of chlorobenzene.
a) ortho-Attack

H
NO, -
b) mctn-Attack Aliphatic and Aromatic

6+No;-&H-+&H
\ -6. :CI:

v
NO,
c1:
:

VI '
NO2
:c]:

61 NO2
Hydrocarbons

In structures 111 and IX, resulting from ortho and para attack, there is a positive
charge on carbon bearing the halogen atom. Through its inductive effect, chlorine
withdraws electrons, making this structure unstable. But there is another factor that
one should not forget. It is known that halogen can share a lone pair of electrons and
accommodate the positive charge, as shown in structures IV and X, for ortho and
para attack, respectiveluy. These structures are comparatively stable.No such structure
is posible when the electrophiles attack on meta position. Structuers IV (in ortho attack)
and X (in para attack) outweigh the instability rendered by structures I11 and IX.
Therefore, attack at ortho and para position is prefered.
SAQ 5
Predict the major and minor products ofthe following :
a) Nitration of bromobenzene

b) Nitration of nitrobenzene

c) Bromination of nitrobenzene
............................................................................................
d) Chlorination of phenol
15.8 POLYNUCLEAR HYDROCARBONS
Polylluclear hydrocarbon is an assembly of more than one benzene ring in the molecule.
Depending upon the mode of attachment of various rings, the polynuclear aromatic
hydrocarbons may be classified into two broad classes:(i) isolated benzenoid
hydrocarbon, and (ii) condensed or fused benzenoid hydrocarbons.

i) Isoated benzenoid hydrocarbon: In isolated systems, two or more rings are

joined to each other either directly or through carbon chain. Some common
exaniples are biphenyl, diphenylrnethane and triphenylmethane.

ii) Condensed o r fused benzenoid hydrocarbons:The condensed or fused

benzenoid hydrocarbons are those in which two or Inore benzene rings are
fused together at the ortho position in such a way that each pair of rings shares
two carbon~.~fhey include compounds like naphthalene, inthracene; phenanthrene
etc.

Naphthalene Anthracene Phenanthrene

The condensed polyuclear hydrocarbons is by far the larger and the more important
group. A !arge number of them have been found to possess carcinogenic (cancer
producing) activity. In this unit we will discuss the chemistry of naphthalene only.

15.8.1 Reactions of Naphthalene

Naphthalene is the parent compund of polynuclear hydrocarbons. Naphthalene,m.p.355
K, is a colourless volatile crysthiline solid.
Naphthalene has three resonance hybrid structures. The bonds are not all of the same
length, but are close to the benzene value of 139.7 pm.
r 7

L d

@ow can we explain the aromaticity of naphthalene? The above structure of naphthalene
shows that it has 10 n electrons and 10 is the Huckel number which indicates that
naphthalene should be an aromatic molecule.
Like benzene, naphthalene undergoes usual electrophilic substitution reactions. It also
undergoes oxidation or reduction more readily than benzene, Some important reactions
of naphthalene are given in Table 15.4.
s
 Aliphatic and Aromatic
Table 15.4 : Electrophilic substitution reactions of naphthalene
Hydrocarbons
Reaction Remarks
1) Nitration

&
At higher
temperature, a

+ J3N03 + H2S04 , mixture of 1, 5- and

I,*-
dinitronaphthalene
I -n~tmnaphthalene
are formed
2) ' Halogenation
1) 1-Chloro-

&
Br
naphthalene can
form in presence of
,-. FeCl,
2) Only
I -bromonaphthalene 1-substitution takes
place
3) Sulphonation

&
S0,H
At 435 K, 2-
naphthalenesulphonic
+H2S0, x5K , acid IS the main
product
I -naphthalenesulphonic
acid
4) Friedel-Crafts Alkylation

&+m
The proportion of
-
C H ~1 and 2-

m + C H 3 I *ICh, products
substituted
depends
I-methylnaphthalene 2-methylnaphthalene On the
of the
reagents

5) Friedel-Crafts Acylation
0
II 0
II

a + C H 3
0
II
C C I
&+yJ
a \ / \ /
The proportion of
CCH, 1- and 2-
products
substituted -
depends
on the solvent used
1-naphthyl methyl 2-naphthyl methyl
ketone ketone

Polynuclear hydrocarbons are more reactive towards electrophilic attack than benzene.
Naphthalene undergoes a number of usual electrophilic substitution, reactions,such
as nitration, halogenation, sulphonation, Friedel-Crafts alkylation, Friedel-Crafts

The mechanism for naphthalene substitution reaction is sj'milar to that of benzene

substitution.
. The first substituent goes to 1-position(a-position); that means, the 1-position ib more
reactive than the 2-position (P-Position) You can ask why"it is so.
To understand this, let us examine the resonance structures of the tpvo intermediate
carbocations resulting from the respective attacks.
Substitution at 1-position
E .

qqJ$
a-substitut,ed
product
Cheniistry ofcarbon Resonance structure of carbocation
Compounds

Substitution at 2-position

Resonance structure of carbocation

[n both cases, the positive charge can be distributed to five different positions, but
these carbocations are not equivalent in energy. In the first case, the first two structures
have their benzene ring intact and are consequently more stable than the remaining
three sturctuns. In the second case, only one resonance structure has a benzenoid
ring intact. The resulting resonance hybrid has higher energy in the second case than
in the first case.The resulting resonance hybrid has higher energy in the second case
than in the first case. The intermediate carbocation in the first case is more stabilised
by resonance, and its transition state is of lower energy. For this reason the intermediate
in the first case is formed faster and 1-position is more reactive.

SAQ - 6
Why 1 - position in naphthalene is more reactive towards electrophilic substitution
reactions?
 Aliphatic and Aromatic
15.9 SUMMARY **-.A- ----
LA--
nyurucaruults

- The main reactions of alkenes are electrophilic addition reactions. These reac-
I
. .
tiolis include addition of halogens, alkylhalides, and water etc.
Addition of HX, H, or X, to conjugated dienes give normal 1,Zaddition product
and abnorlnal 1,4-additih product.
Terminal alky'nes are more acidic tlian alkanes or alkenes
Addition reaction of alkenes and alkynes follow Markownikoff's rule.
-- The main reactions of aromatic compounds are electrophilic substitution reac-
tions. e.g, nitration, halogenation, Friedel-Crafts al.kylation etc.
Group attached to the aromatic ring affect the reactivity of tlie ring for further
substit~~tion and also determine the orientation of further substitution.
'The electron-donating - substiluents, when attached to benzene, have ortho and
para directing influence while electron-withdrawing substituents have meta di-
recting influence. ,
In polynuclear hydrocarbons 1 position is more reactive towards electrophilic
substitution.

15.10 TERMINAL QUESTIONS

I. What is resonance energy? Explain with the help of an example.

2. What do you understand by activating and deactivating group, Explain.

3. Suggest the structure of alkenes I alkynes that give the following product's:
(9 *3'- chloro - 2,3 - dimethylbutane

' (ii) HBr ) 1- Bromopropanenitrile

4. What is Markownikoffs rule? Explain

5. Which of the following compounds are aromatic. Give reason.